Handbook of Practical X-Ray Fluorescence Analysis

899 Pages·2006·15.051 MB·English

by  B. Beckhoff,N. Langhoff,B. Kanngiefer,R. Wedell,H. Wolff

HandbookofPracticalX-RayFluorescenceAnalysis
B. Beckhoff B. Kanngießer
N. Langhoff R. Wedell H. Wolff
(Eds.)
Handbook
of Practical
X-Ray Fluorescence
Analysis
With385Figuresand53Tables
123
Dr.BurkhardBeckhoff
Physikalisch-TechnischeBundesanstalt,X-raySpectrometry
Abbestr.2–12,10587Berlin,Germany
E-mail:[email protected]
Dr.habil.BirgitKanngießer
TechnischeUniversita¨tBerlin,Fakulta¨t2,Institutfu¨rAtomarePhysikundFachdidaktik
Hardenbergstr.36,10623Berlin,Germany
E-mail:[email protected]
ProfessorDr.NorbertLanghoff
IfG- I nstitute fo r S cientific
Instruments GmbH
Rudower Chaussee 29/31, 12489
Berlin, Germany
E-mail:[email protected]
Dr.sc.nat.ReinerWedell
Dr.sc.nat.HelmutWolff
Institutfu¨rAngewandtePhotonike.V.
RudowerChaussee29/31,12489Berlin,Germany
E-mail:[email protected],[email protected]
LibraryofCongressControlNumber:2005934096
ISBN-103-540-28603-9SpringerBerlinHeidelbergNewYork
ISBN-13978-3-540-28603-5SpringerBerlinHeidelbergNewYork
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Preface
X-Ray fluorescence analysis (XRF) has developed into a well-established
multi-elemental analysis technique with a very wide field of practical appli-
cations, especially those requiring nondestructive analytical methods. Over a
long period of time, steady progress of XRF was made, both methodological
and instrumental. Within the last decade, however, advancements in tech-
nology, software development, and methodologies for quantification have pro-
vided an impetus to XRF research and application, leading to striking new
improvements. The recent technological advances, including table-top instru-
ments that take advantage of novel low-power micro-focus tubes, novel X-ray
optics and detectors, as well as simplified access to synchrotron radiation,
have made it possible to extend XRF to low Z elements and to obtain two-
and three-dimensional information from a sample on a micrometer-scale. The
development of portable and hand-held devices has enabled a more flexible
use of XRF in a variety of new situations, such as archaeometry and process
control.Furthermore,synchrotronradiationprovideshighexcitationfluxand
even speciation capabilities due to energetically tunable radiation.
Because of these recent advancements, the editors decided to compile a
practicalhandbookofXRFasaresourceforscientistsandindustrialusersthat
providesenoughinformationtoconceiveandsetupmodernXRFexperiments
foruseinawiderangeofpracticalapplications.Additionally,selectedsections
consistofaconcisesummaryofbackgroundinformationforreaderswhowish
to gain a more in-depth understanding of the topics without conducting a
lengthy search of the literature. The present handbook is not intended to
be a textbook with interdependent chapters, rather a reference in which the
information in each section is largely self-contained. In this way, the reader is
not required to read the handbook from cover to cover, but can refer to any
section without a lot of additional background.
The handbook is organized as follows. The first chapter provides a histor-
ical account of XRF and an introduction reflecting the extension of XRF to
modern fields of methodology and applications. Chapters 2, 3, and 4 follow
thepathofaphotoninanXRFinstrument,originatingatasource(2),being
VI Preface
modifiedbyanoptic(3),andregisteredbyadetector(4).Chapter5dealswith
the various aspects of quantifying the spectra obtained from a sample by this
instrument. Expert information on how to prepare the sample is the theme
of Chapter 6. Chapter 7 is devoted to a variety of applications: micro-, trace,
andlayeranalysis;environmental,geological,archaeometric,forensic,andbio-
medical applications; and process control. The handbook concludes with a
discussiononsafetyregulationsandusefullinkstophysicaldata(Chapter8).
We would like to take this opportunity to express our gratitude to all of
the authors, especially those who completed their contributions at an early
stage in the preparation of this book and patiently awaited its completion.
Our thanks also go to Katherine Roegner of the Technical University, Berlin
for her support in matters of language.
We hope you enjoy this practical handbook and that it contributes to the
continued development of XRF. We also hope that it encourages and inspires
newcomers to the field in exploring the multifaceted aspects of XRF.
Burkhard Beckhoff,
Birgit Kanngießer,
Norbert Langhoff,
Berlin, Reiner Wedell
November 2005 and Helmut Wolff
Contents
1 Introduction
T. Arai ......................................................... 1
1.1 The Discovery of X-Rays and Origin
of X-Ray Fluorescence Analysis................................ 1
1.2 Historical Progress of Laboratory X-Ray Fluorescence
Spectrometers ............................................... 4
1.3 Measurement of Soft and Ultrasoft X-Rays...................... 8
1.3.1 X-Ray Tubes for Soft and Ultrasoft X-Rays............... 8
1.3.2 Scientific Research Work on Soft and Ultrasoft X-Rays..... 9
1.3.3 Synthetic Multilayer Analyzers.......................... 9
1.3.4 Total Reflection Mirrors................................ 13
1.4 Analytical Precision and Accuracy
in X-Ray Fluorescence Analysis................................ 15
1.4.1 Correction of Matrix Element Effects .................... 16
1.4.2 Quantitative Analysis of Heat Resistance
and High Temperature Alloys ........................... 19
1.4.3 Segregation Influencing Analytical Accuracy .............. 25
1.5 Concluding Remarks ......................................... 26
References ...................................................... 26
2 X-Ray Sources
2.1 Introduction
N. Langhoff and A. Simionovici.................................... 33
2.2 X-Ray Tubes
V. Arkadiev, W. Knu¨pfer and N. Langhoff .......................... 36
2.2.1 Basic Physical Principles ............................... 36
2.2.2 Technology of the Components.......................... 38
2.2.3 Vacuum Envelope of X-Ray Tubes....................... 46
2.2.4 Tube Housing Assembly................................ 47
VIII Contents
2.2.5 Modern X-Ray Tubes .................................. 47
2.2.6 Some Applications..................................... 52
2.3 Radioisotope Sources
T. Cˇech´ak and J. Leonhardt ....................................... 54
2.3.1 Basic Physical Principles ............................... 55
2.3.2 Radioisotope Sources .................................. 57
2.3.3 Production of Radioactive Sources....................... 63
2.3.4 Radiation Protection Regulations........................ 64
2.4 Synchrotron Radiation Sources
A. Simionovici and J. Chavanne .................................. 66
2.4.1 SR Basics ............................................ 66
2.4.2 Storage Ring Description............................... 67
2.4.3 Generation of SR...................................... 68
2.4.4 SRW Package......................................... 72
References ...................................................... 80
3 X-Ray Optics
3.1 Introduction
A. Erko......................................................... 85
3.2 Mirror Optics
V. Arkadiev and A. Bjeoumikhov................................... 89
3.2.1 Total External Reflection Mirrors........................ 89
3.2.2 Capillary Optical Systems .............................. 89
3.3 Diffraction Optics – Elements of Diffraction Theory
A. Erko.........................................................111
3.3.1 Electromagnetic Wave Propagation ......................111
3.3.2 Fraunhofer Approximation..............................113
3.3.3 Fresnel Approximation .................................113
3.3.4 Bragg Diffraction......................................115
3.4 Optics for Monochromators
A. Antonov, V. Arkadiev, B. Beckhoff, A. Erko, I. Grigorieva,
B. Kanngießer and B. Vidal.......................................115
3.4.1 Diffraction Gratings ...................................115
3.4.2 Multilayers for X-Ray Optics ...........................129
3.4.3 HOPG-based Optics ...................................143
3.4.4 Laterally Graded SiGe Crystals .........................157
3.5 Focusing Diffraction Optics
A. Erko.........................................................167
3.5.1 Zone Plates...........................................167
3.5.2 Reflection Zone Plate and Bragg–Fresnel Optics...........179
3.5.3 Bragg–Fresnel Holographic Optics .......................185
3.6 Refraction X-Ray Optics
A. Erko.........................................................187
3.6.1 Compound Refractive Lens .............................187
References ......................................................190
Contents IX
4 X-Ray Detectors and XRF Detection Channels
4.1 Introduction
F. Scholze.......................................................199
4.2 X-Ray Detectors and Signal Processing
A. Longoni and C. Fiorini ........................................203
4.2.1 Introduction ..........................................203
4.2.2 Basic Properties of X-Ray Detectors .....................203
4.2.3 Classification of the Most Commonly Used X-Ray
Detectors.............................................216
4.2.4 Semiconductor Detectors ...............................218
4.2.5 Silicon Drift Detectors .................................222
4.2.6 Basics of Signal Electronics .............................235
4.2.7 Shape Factors of some Filtering Amplifiers ...............249
4.2.8 Auxiliary Functions....................................252
4.2.9 Appendix 1 – The Laplace Transform ....................256
4.2.10 Appendix 2 – Calculation of the ENC....................257
4.2.11 Appendix 3 – Digital Pulse Processing ...................259
4.3 High Resolution Imaging X-Ray CCD Spectrometers
L. Stru¨der, N. Meidinger and R. Hartmann .........................262
4.3.1 Introduction ..........................................262
4.3.2 Fully Depleted Backside Illuminated pn-CCDs ............264
4.3.3 Frame Store pn-CCDs for ROSITA, and XEUS............277
4.3.4 Conclusion ...........................................284
4.4 Wavelength Dispersive XRF and a Comparison with EDS
N. Kawahara and T. Shoji ........................................284
4.4.1 Dispersion Materials for WDXRF .......................285
4.4.2 Detectors and Electronics ..............................288
4.4.3 Optics Used for the WD Spectrometer and its
Components ..........................................293
4.4.4 Types of WDXRF Spectrometer.........................296
4.4.5 Selected Applications Suitable for WDXRF...............299
4.4.6 Comparison of WDXRF and EDXRF ....................301
References ......................................................302
5 Quantitative Analysis
5.1 Overview
M. Mantler .....................................................309
5.2 Basic Fundamental Parameter Equations
M. Mantler .....................................................311
5.2.1 Fundamental Parameter Equations for Bulk Materials......312
5.2.2 Direct Excitation......................................317
5.2.3 Indirect Excitation ....................................322
5.2.4 Use of Standards ......................................325
X Contents
5.3 Matrix Correction Methods and Influence Coefficients ............327
5.3.1 The Nature of Influence Coefficients
M. Mantler .................................................327
5.3.2 The Lachance–Traill Algorithm
J.P. Willis, G.R. Lachance....................................335
5.3.3 The Claisse–Quintin Algorithm
J.P. Willis, G.R. Lachance....................................340
5.3.4 The COLA Algorithm
J.P. Willis, G.R. Lachance....................................343
5.3.5 The de Jongh Algorithm
B.A.R. Vrebos...............................................345
5.3.6 The Broll–Tertian Algorithm
K.-E. Mauser ...............................................347
5.3.7 The Japanese Industrial Standard Method
N. Kawahara................................................349
5.3.8 The Fundamental Algorithm
R.M. Rousseau ..............................................350
5.4 Compensation Methods.......................................358
B.A.R. Vrebos ...................................................358
5.4.1 Internal Standards.....................................358
5.4.2 Standard Addition Methods ............................361
5.4.3 Dilution Methods .....................................362
5.4.4 Scattered Radiation – Compton Scatter ..................363
5.5 Thin and Layered Samples
P.N. Brouwer ...................................................369
5.5.1 Direct Excitation by Polychromatic Sources...............369
5.5.2 Indirect Excitation by Polychromatic Sources .............371
5.5.3 Back-Calculation Schemes ..............................375
5.5.4 Solvability............................................376
5.5.5 Applications ..........................................377
5.6 Complex Excitation Effects and Light Elements
N. Kawahara ....................................................379
5.6.1 Indirect Excitation Processes in the Low Energy Region....379
5.6.2 Secondary Excitation by Electrons.......................379
5.6.3 Cascade Effect ........................................382
5.7 Standardless Methods
K.-E. Mauser ...................................................384
5.7.1 Introduction ..........................................384
5.7.2 Semiquantitative Analysis ..............................384
5.7.3 Requirements for a Standardless Method .................385
5.8 Monte Carlo Methods
M. Mantler .....................................................394
5.9 Errors and Reliability Issues
M. Mantler .....................................................395
5.9.1 Mathematical Treatment of Statistical Errors .............397
Contents XI
5.9.2 Counting Statistics ....................................398
5.9.3 Detection Limits ......................................398
5.10 Standardized Methods
K.-E. Mauser ...................................................400
5.10.1 Introduction ..........................................400
5.10.2 General Features of Standardized Methods ...............400
5.10.3 Standardized Methods Versus Universal Calibrations
and Standardless Methods..............................403
5.10.4 Summary.............................................403
Symbols and Terminology.........................................404
References ......................................................407
6 Specimen Preparation
J. Injuk, R. Van Grieken, A. Blank, L. Eksperiandova and V. Buhrke ..411
6.1 Introduction ................................................411
6.2 Liquids.....................................................412
6.2.1 Direct Analysis of Liquids and Solutions..................412
6.2.2 Conversion of Liquids into Quasi-Solid Specimens .........413
6.2.3 Conversion of Liquids into Organic Glassy
Polymer Specimens ....................................414
6.2.4 Conversion of Liquids into Thin Films ...................414
6.2.5 Analysis of Solutions after Preconcentration
of Microimpurities.....................................415
6.3 Solid Specimens .............................................419
6.3.1 Metallic Specimens ....................................419
6.3.2 Powder Specimens.....................................421
6.3.3 Fused Specimens ......................................424
6.4 Biological Samples ...........................................426
6.5 Aerosol and Dust Specimens ..................................427
6.6 Standards...................................................428
References ......................................................429
7 Methodological Developments and Applications
7.1 Micro X-Ray Fluorescence Spectroscopy
B. Kanngießer and M. Haschke....................................433
7.1.1 Introduction ..........................................433
7.1.2 General Description of Micro-XRF Laboratory Units.......434
7.1.3 Applications of Micro X-Ray Fluorescence Analysis........442
7.1.4 3D Micro X-Ray Fluorescence Spectroscopy ..............462
7.2 Micro-XRF with Synchrotron Radiation
A. Simionovici and P. Chevallier ..................................474
7.2.1 Introduction ..........................................474
7.2.2 The General Setup ....................................475
7.2.3 Quantitative Aspect ...................................481
7.2.4 Elemental Mapping....................................484
7.2.5 Examples of Application ...............................488